Organic semiconductor element, polymer, organic semiconductor composition, and organic semiconductor film

ABSTRACT

Provided are an organic semiconductor element including an organic semiconductor film that includes a polymer having a repeating unit represented by the following Formula (1), the polymer, and an organic semiconductor composition and an organic semiconductor film including the polymer.In the formula, Y1 represents O, S, or Se. R11 to R14 each independently represent a substituent. a and b each independently represent an integer of 0 to 3, and r and s each independently represent an integer of 0 to 2. A10 represents an aromatic heterocyclic group. m10 represents an integer of 1 to 12.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No. PCT/JP2017/012174 filed on Mar. 24, 2017, which claims priorities under 35 § 119 (a) to Japanese Patent Application No, JP2016-074079 filed on Apr. 1, 2016. Each of the above applications is hereby expressly incorporated by reference, in its entirety, into the present application.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to an organic semiconductor element, and a polymer, an organic semiconductor composition, and an organic semiconductor film used in the organic semiconductor element.

2. Description of the Background Art

In a display such as a liquid crystal display or an organic electroluminescence display, a device using a logical circuit such as a radio frequency identifier (RFID) or a memory, a solar cell, or the like, a semiconductor element is used. In particular, an organic semiconductor element including an organic semiconductor film can realize weight reduction or cost reduction and also has excellent flexibility. Therefore, the organic semiconductor element including an organic semiconductor film is superior to an inorganic semiconductor element including an inorganic semiconductor film.

As an organic compound forming the organic semiconductor film, an organic polymer compound or a low molecular weight compound is considered. As the organic polymer compound, for example, a polymer compound having a structural unit derived from a fused ring compound having a 5-membered ring structure between two different heterocycles is disclosed (JP2015-172140A). In addition, as the low molecular weight compound, for example, a dinaphthothiophene compound is disclosed (JP2015-048346A and JP2013-197193A).

SUMMARY OF THE INVENTION

The performance of the above-described display or the like has been rapidly improved, and for an organic semiconductor element mounted on the display or the like, for example, high performance and uniformity in which a variation in performance is reduced are required.

Further, an organic semiconductor element or an organic semiconductor film may be exposed to a high-temperature environment. Therefore, heat resistance with which a carrier mobility can be maintained even under high temperature conditions is required. Examples of the high-temperature environment include high temperature conditions during the manufacturing of an organic semiconductor element, further, the use of an organic semiconductor element in a high-temperature environment.

However, an organic semiconductor element of the related art is not sufficient in carrier mobility, uniformity thereof, and heat resistance and has a room for improvement.

An object of the present invention is to provide an organic semiconductor element having high carrier mobility, uniformity thereof, and high heat resistance, and a polymer, an organic semiconductor composition, and an organic semiconductor film used in the organic semiconductor element.

As a result of thorough investigation, the present inventors found that a polymer that includes a repeating unit having a fused ring structure derived from a dinaphtho chalcogenophene compound and a specific conjugated group can be used as an organic semiconductor film in an organic semiconductor element. Further, the present inventors found that, by using this polymer as an organic semiconductor film, high carrier mobility, uniformity thereof, and high heat resistance can be simultaneously obtained. The present invention has been completed based on the above findings as a result of repeated investigation.

The object of the present invention is achieved by the following means.

<1> An organic semiconductor element comprising:

an organic semiconductor film that includes a polymer having a repeating unit represented by the following Formula (1),

in Formula (1),

Y¹ represents an oxygen atom, a sulfur atom, or a selenium atom,

R¹¹ to R¹⁴ each independently represent a substituent,

a and b each independently represent an integer of 0 to 3,

r and s each independently represent an integer of 0 to 2,

A¹⁰ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and

m¹⁰ represents an integer of 1 to 12.

<2> The organic semiconductor element according to <1>,

in which the repeating unit is represented by the following Formula (2),

in Formula (2),

Y¹, R¹¹ to R¹⁴, a, b, r, and s have the same definitions as Y¹, R¹¹ to R¹⁴, a, b, r, and s in Formula (1), respectively,

A¹¹ and A¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group other than aromatic heterocyclic groups represented by the following Formulae (A-1) to (A-12), a vinylene group, or an ethynylene group,

A¹² represents an aromatic heterocyclic group represented by any one of the following Formulae (A-1) to (A-12),

m¹¹ and m¹³ each independently represent an integer of 0 to 4,

m¹² represents an integer of 0 to 4, and

the sum of m¹¹, and m¹², and m¹³ is 1 or more,

in Formulae (A-1) to (A-12),

X^(A)'s each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR^(X),

R^(N) and R^(X) each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain or a group represented by the following Formula (1-1),

Y^(A)'s each independently represent an oxygen atom or a sulfur atom,

Z^(A)'s each independently represent CR^(A2) or a nitrogen atom,

W^(A)'s each independently represent C(R^(A2))₂, NR^(A1), a nitrogen atom, CR^(A2), an oxygen atom, a sulfur atom, or a selenium atom,

R^(A1)'s each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, a group represented by the following Formula (1-1), or a single bond,

R^(A2)'s each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, or a single bond,

R^(A3)'s each independently represent a hydrogen atom or a substituent, and

* represents a binding site to another group forming the repeating unit, and

in Formula (1-1),

L_(a) represents an alkylene group having 1 to 20 carbon atoms which may have at least one of —O—, —S—, or —NR^(1S)— in a carbon chain,

Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

L_(b) represents an alkyl group having 1 to 100 carbon atoms which may have at least one of —O—, —S—, or —NR^(2S)— in a carbon chain,

R^(1S) and R^(2S) each independently represent a hydrogen atom or a substituent,

1 represents an integer of 1 to 5, and

* represents a binding site to a ring-constituting nitrogen atom in Formula (A-1) or (A-2), a nitrogen atom in NR^(X) of X^(A), or a nitrogen atom in NR^(A1) of W^(A).

<3> The organic semiconductor element according to <2>,

in which m¹² represents an integer of 1 to 4.

<4> The organic semiconductor element according to <2> or <3>,

in which -(A¹¹)m¹¹- and -(A¹³)m¹³- are each independently represented by the following Formula (Ar-1),

in Formula (Ar-1),

X^(d) represents an oxygen atom, a sulfur atom, a selenium atom, or NR^(D1),

Z^(d)'s each independently represent a nitrogen atom or CR^(D2),

R^(D1) and R^(D2) represent a hydrogen atom or a substituent,

m^(d) represents an integer of 1 to 4, and

* represents a binding site to another group forming the repeating unit.

<5> The organic semiconductor element according to <4>,

in which X^(d) represents a sulfur atom, and

all the Z^(d)'s represent CR^(D3),

<6> The organic semiconductor element according to any one of <1> to <5>,

in which the organic semiconductor element is an organic thin film transistor element.

<7> A polymer comprising:

a repeating unit represented by the following Formula (1),

in Formula (1),

Y¹ represents an oxygen atom, a sulfur atom, or a selenium atom,

R¹¹ to R¹⁴ each independently represent a substituent,

a and b each independently represent an integer of 0 to 3,

r and s each independently represent an integer of 0 to 2,

A¹⁰ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and

m¹⁰ represents an integer of 1 to 12.

<8> The polymer according to <7>,

in which the repeating unit is represented by the following Formula (2),

in Formula (2),

Y¹, R¹¹ to R¹⁴, a, b, r, and s have the same definitions as Y¹, R¹¹ to R¹⁴, a, b, r, and s in Formula (1), respectively.

A¹¹ and A¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group other than aromatic heterocyclic groups represented by the following Formulae (A-1) to (A-12), a vinylene group, or an ethynylene group,

A¹² represents an aromatic heterocyclic group represented by any one of the following Formulae (A-1) to (A-12),

m¹¹ and m¹³ each independently represent a integer of 0 to 4,

m¹² represents an integer of 0 to 4, and

the sum of m¹¹, m¹², and m¹³ is 1 or more.

in Formulae (A-1) to (A-12),

X^(A)'s each independently represent oxygen atom, a sulfur atom, a selenium atom, or NR^(X),

R^(N) and R^(X) each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain or a group represented by the following Formula (1-1),

Y^(A)'s each independently represent an oxygen atom or a sulfur atom,

Z^(A)'s each independently represent CR^(A2) or a nitrogen atom,

W^(A)'s each independently represent C(R^(A2))₂, NR^(A1), a nitrogen atom, CR^(A2), an oxygen atom, a sulfur atom, or a selenium atom,

R^(A1) 's each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, a group represented by the following Formula (1-1), or a single bond,

R^(A2)'s each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, or a single bond,

R^(A3)'s each independently represent a hydrogen atom or a substituent, and

* represents a binding site to another group forming the repeating unit, and

in Formula (1-1),

L_(a) represents an alkylene group having 1 to 20 carbon atoms which may have at least one of —O—, —S—, or —NR^(1S)— in a carbon chain,

Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms,

L_(b) represents an alkyl group having 1 to 100 carbon atoms which may have at least one of —O—, —S—, or —NR^(2S)— in a carbon chain,

R^(1S) and R^(2S) each independently represent a hydrogen atom or a substituent,

1 represents an integer of 1 to 5, and

* represents a binding site to a ring-constituting nitrogen atom in Formula (A-1) or (A-2), a nitrogen atom in NR^(X) of X^(A), or a nitrogen atom in NR^(A1) of W^(A).

<9> The polymer according to <8>,

in which m¹² represents an integer of 1 to 4.

<10> The polymer according to <8> or <9>,

in which -(A¹¹)m¹¹- and -(A¹³)m¹³- are each independently represented by the following Formula (Ar-1),

in Formula (Ar-1),

X^(d) represents an oxygen atom, a sulfur atom, a selenium atom, or NR^(D1),

Z^(d)'s each independently represent a nitrogen atom or CR^(D2),

R^(D1) and R^(D2) represent a hydrogen atom or a substituent,

m^(d) represents an integer of 1 to 4, and

* represents a binding site to another group forming the repeating unit.

<11> The polymer according to <10>,

in which X^(d) represents a sulfur atom, and

all the Z^(d)'s represent CR^(D2).

<12> An organic semiconductor composition comprising: the polymer according to any one of <7> to <11>; and

a solvent.

<13> An organic semiconductor film comprising:

the polymer according to any one of <7> to <11>.

The present invention can provide an organic semiconductor element having high carrier mobility, uniformity thereof, and high heat resistance. In addition, the present invention can provide a polymer used in the organic semiconductor element having the excellent characteristics, and an organic semiconductor composition and an organic semiconductor film including the polymer.

The above-described and other characteristics and advantageous effects of the present invention will be clarified from the following description appropriately with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view showing a bottom gate-bottom contact type organic thin film transistor element as an example of a semiconductor element according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view showing a bottom gate-top contact type organic thin film transistor element as an example of the semiconductor element according to the embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In this specification, numerical ranges represented by “to” include numerical values before and after “to” as lower limit values and upper limit values.

The meaning of compounds described in this specification include not only the compounds themselves but also salts and ions thereof in addition, within a range where a desired effect does not deteriorate, a part of the structure may be changed.

In addition, in a case where it is not clearly described that a compound is substituted or unsubstituted, this compound has any substituent within a range where a desired effect does not deteriorate. The same shall be applied to a substituent, a linking group, or the like (hereinafter, referred to as “substituent or the like”).

In this specification, in a case where a plurality of substituents or the like represented by a specific reference numeral are present or a plurality of substituents or the like are simultaneously defined, the respective substituents or the like may be the same as or different from each other unless specified otherwise. The same shall be applied to definition of the number of substituents or the like. In addition, in a case where a plurality of substituents or the like are close to (in particular, adjacent to) each other, the substituents or the like may be linked to each other to form a ring unless specified otherwise.

In the present invention, in a case where a plurality of repeating units represented by the same chemical structure are present in a polymer, the respective repeating units present in the polymer may be the same as or different from each other. The same shall be applied to each group forming the repeating unit.

In addition, in a case where the number of carbon atoms in a group is limited, the number of carbon atoms in this group represents the total number of carbon atoms including substituents unless specified otherwise.

In the present invention, in a case where a group can form an acyclic skeleton and a cyclic skeleton, this group includes a group having an acyclic skeleton and a group having a cyclic skeleton unless specified otherwise. For example, an alkyl group includes a linear alkyl group, a branched alkyl group, and a cycloalkyl group. In a case where a group can form a cyclic skeleton, the lower limit of the number of atoms of the group forming a cyclic skeleton is not limited to the lower limit of the number of atoms specifically described regarding this group, and is 3 or more and preferably 5 or more.

A preferable embodiment of the present invention will be described below, but the present invention is not limited thereto.

[Polymer]

First, a polymer according to the embodiment of the present invention will be described.

The polymer (organic semiconductor) according to die embodiment of the present invention includes a repeating unit represented by the following Formula (1). This polymer is a copolymer that includes a repeating unit having a group derived from a dinaphtho chalcogenophene compound in which two naphthalene rings and a chalcogenophene ring are fused having at least one group represented by the following A¹⁰. This copolymer is preferably a π-conjugated polymer.

In a case where the polymer according to the embodiment of the present invention has an aromatic heterocyclic group represented by A¹² in Formula (2) shown below, the polymer may also be a so-called “D-A polymer” including an electron-donating unit (donor unit) and an electron-accepting unit (acceptor unit). In this ease, the group derived from the dinaphtho chalcogenophene compound functions as the donor unit, and the aromatic heterocyclic group represented by A¹² functions as the acceptor unit. In a case where the polymer according to the embodiment of the present invention has a group represented by A¹¹ or A¹³ in Formula (2) shown below, these groups function as the donor unit.

In Formula (1), Y¹ represents an oxygen atom, a sulfur atom, or a selenium atom. Y¹ represents preferably an oxygen atom o a sulfur atom and more preferably a sulfur atom.

R¹¹ to R¹⁴ each independently represent a substituent.

The substituent which may be used as R¹¹ to R¹⁴ is not particularly limited. Preferable examples of the substituent include an alkyl group which may have at least one of —O—, —S—, or —NR¹— in a carbon chain (for example, preferably an alkyl group having 1 to 35 carbon atoms or an alkoxy group having 1 to 35 carbon atoms and more preferably an alkyl group having 1 to 25 carbon atoms), an alkenyl group (preferably having 2 to 30 carbon atoms), an alkynyl group (preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (having preferably 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably a 5-membered to 7-membered ring; including preferably at least one of an oxygen atom, a nitrogen atom, a sulfur atom, or a selenium atom as a ring-constituting heteroatom), a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and still more preferably a fluorine atom), and a group represented by Formula (1-1) shown below. Among these, the alkyl group is preferable.

In the present invention, examples of the alkyl group having —O— in a carbon chain include a group having —O— in the middle of a carbon-carbon bond, a group (also referred to as “alkoxy group”) having —O— at a terminal of a carbon-carbon bond, and a group having —O— in the middle of and at a terminal of a carbon-carbon bond. The same shall be applied to the alkyl group having —S— or —NR¹— in a carbon chain. In a case where the alkyl group has —O—, —S—, and —NR¹—, the total number of these groups is at least one, and the upper limit thereof is not particularly limited and is, for example, 5.

R¹ represents a hydrogen atom or a substituent. The substituent which may be used as R¹ is not particularly limited and has the same definition as the substituent of R^(1S) and R^(2S) described below.

Adjacent two among, R¹¹ to R¹⁴ may be bonded to each other to form a ring but preferably do not form a ring.

a and b each independently represent an integer of 0 to 3, preferably 0 or 1 and more preferably 0.

r and s each independently represent an integer of 0 to 2, preferably 0 or 1 and more preferably 0.

A¹⁰ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.

The aromatic hydrocarbon group which may be used as A¹⁰ is not particularly limited and may be a monocyclic group or a fused ring group composed of 2 or more rings. From the viewpoint of carrier mobility, it is preferable that the aromatic hydrocarbon group is a monocyclic group. As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 18 carbon atoms is more preferable, and a phenylene group, a naphthylene group, or a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon in which three rings or four rings are fused is still more preferable. Examples of the group obtained by removing two hydrogen atoms from an aromatic hydrocarbon in which three rings or four rings are fused include a group obtained by removing two hydrogen atoms from a fluorene ring, an anthracene ring, a phenanthrene ring, a chrysene ring, or a pyrene ring.

As the aromatic hydrocarbon group, a phenylene group, a naphthylene group, a fluorene ring group, or a pyrene ring group is preferable, and a phenylene group or a naphthylene group is more preferable.

The aromatic heterocyclic group which may be used as A¹⁰ is not particularly and may be a monocyclic group or a fused ring group composed of 2 or more rings. In addition, the aromatic heterocyclic group may be a group in which monocyclic or fused heterocyclic groups are linked through a carbon-carbon double bond. In a case where the aromatic heterocyclic group is a monocyclic group, it is preferable that the number of ring members is 5 to 7. In addition, as the ring-constituting heteroatom included in the aromatic heterocyclic group, a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom is preferable, and a sulfur atom is more preferable.

Examples of the aromatic heterocyclic group include aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) shown below and an aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) shown below.

Examples of the aromatic heterocycle which forms the aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) include a monocycle such as a furan ring, a thiophene ring, a selenophene ring, a pyrrole ring, an oxazole ring, a thiazoh ring, a selenoazole group, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a selenodiazole group, a triazole ring, a pyridine ring, or a triazine ring. In addition, for example, a fused ring composed of at least two of the above-described monocycles or a fused ring composed of at least one of the above-described monocycles and at least one benzene ring or cyclopentadiene ring may also be used. The number of rings composing the fused ring is not particularly limited as long as it is 2 or more, and is preferably 2 to 6. Specific examples of the aromatic heterocycle include a benzodithiophene ring, a dithiophene ring, a trithiophene ring, and a cyclopentadithiophene ring.

As the aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) shown below, a group represented by Formula (Ar-1) shown below is preferable, a furan ring group, a thiophene ring group, or a selenophene ring group is more preferable, and a thiophene ring is still more preferable.

The aromatic hydrocarbon group and the aromatic heterocyclic group each independently may have a substituent. A preferable substituent is not particularly limited, and examples thereof include an alkyl group which may have at least one of —O—, —S—, or —NR¹— in a carbon chain (for example, preferably an alkyl group having 1 to 35 carbon atoms or an alkoxy group having 1 to 35 carbon atoms and more preferably an alkyl group having 1 to 25 carbon atoms), an alkenyl group (preferably having 2 to 30 carbon atoms), an alkynyl group (preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (having preferably 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably a 5-membered to 7-membered ring; including preferably at least one of an oxygen atom, a nitrogen atom, a sulfur atom, or a selenium atom as a ring-constituting heteroatom), a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and still more preferably a fluorine atom), and a group represented by Formula (1-1) shown below. Among these, the alkyl group is preferable.

R¹ is as described above.

The vinylene group which may be used as A¹⁰ may have a substituent and preferably does not have a substituent. The substituent which may be included in the vinylene group has the same definition and the same preferable ranges as the substituent which may be included in the aromatic hydrocarbon group and the aromatic heterocyclic group.

m¹⁰ represents an integer of 1 to 12, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, still more preferably an integer of 1 to 5, and even still more preferably an integer of 1 to 3.

In a case where m¹⁰ represents an integer of 2 or more, a plurality of A¹⁰'s may be the same as or different from each other.

In this case, a combination of A¹⁰'s which may be used in (A¹⁰)m¹⁰ is not particularly limited, and the respective groups may be appropriately selected and combined. For example, an aspect including at least one (preferably 1 to 4) aromatic heterocyclic group represented by any one of Formulae (A-1) to (A-12) shown below is preferable. and an aspect including an aromatic hydrocarbon group and at least one (preferably 2 or more, more preferably 2 to 8, and still more preferably 2 to 6) aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) shown below is more preferable.

It is preferable that the repeating unit represented by Formula (1) is represented by the following Formula (2).

In Formula (2), Y¹, R¹¹ to R¹⁴, a, b, r, and s have the same definitions and the same preferable ranges as Y¹, R¹¹ to R¹⁴, a, b, r, and s in Formula (1), respectively.

A¹² represents an aromatic heterocyclic group represented by any one of the following Formulae (A-1) to (A-12). In each of the following formulae, represents a binding site to another group forming the repeating unit represented by Formula (2).

In Formula (A-6) and Formula (A-9), a round broken line in a 5-membered ring or a 6-membered ring represent an aromatic ring in the 5-membered ring or the 6-membered ring.

In Formulae (A-1) to (A-12), X^(A)'s each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR^(X), and preferably a sulfur atom or NR^(X).

R^(N) and R^(X) each independently represent an alkyl group which may lave at least one of —O—, —S—, or —NR^(A3)— in a carbon chain or a group represented by Formula (1-1) shown below. The alkyl group which may be used as R^(N) and R^(X) has the same definition and the same preferable ranges as the alkyl group which may be used as R^(A1) described below. R^(A3) will be described below.

Y^(A)'s each independently represent an oxygen atom or a sulfur atom and preferably an oxygen atom.

Z^(A)'s each independently represent CR^(A2) or a nitrogen atom and preferably CR^(A2).

R^(A)'s each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, or a single bond. It is preferable that R^(A2) represents a hydrogen atom or a single bond. In Formula (A-2) and Formula (A-8), R^(A2) does not represent a single bond. In a case where R^(A2) represents a halogen atom, as the halogen atom, a fluorine atom, a chlorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a fluorine atom is more preferable. The alkyl group which may be used as R^(A2) has the same definition and the same preferable ranges as the alkyl group which may be used as R^(A1) described below. R^(A3) will be described below.

In a case where R^(A2) in CR^(A2) represents a single bond, a C atom in CR^(A2) is a binding site (in each of the formulae, represented by *) in each of (A-5), (A-10), and (A-11).

Specifically, in each of two ring structures including Z^(A) in Formula (A-5) and Formula (A-10), one Z^(A) represents CR^(A2), in which R^(A2) represents a single bond. CR^(A2) (carbon atom) including a single bond represents a binding site represented by * in each of the formulae. In addition, in Formula (A-11), two of eight Z^(A)'s represent CR^(A2), in which R^(A2) represent a single bond. The two CR^(A2)'s (carbon atom) including a single bond represent a binding site represented by * in Formula (A-11).

In the repeating unit represented by Formula (2), the binding site refers to a binding site to another group forming the repeating unit represented by Formula (2). The other group refers to the group derived from the dinaphtho chaleogenophene compound or a group represented by A¹¹, A¹², or A¹³ in the repeating unit represented by Formula (2).

W^(A)'s each independently represent C(R^(A2))₂, NR^(A1), a nitrogen atom, CR^(A2), an oxygen atom, a sulfur atom, or a selenium atom, preferably C(R^(A2))₂, CR^(A2), or a sulfur atom, and more preferably CR^(A2) or a sulfur atom.

R^(A1)'s each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, a group represented by Formula (1-1) shown below, or a single bond. As R^(A1), the alkyl group or the group represented by Formula (1-1) shown below is preferable. The alkyl group which may be used as R^(A1) may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 35 and more preferably 1 to 25.

R^(A2) in W^(A) has the same definition and the same preferable ranges as R^(A2) in Z^(A).

R^(A3) represents a hydrogen atom or a substituent. The substituent which may be used as R^(A3) is not particularly limited and has the same definition and the same preferable ranges as the substituent of R^(1S) and R^(2S) described below.

In each of two ring structures including W^(A) in Formula (A-6), one W^(A) adopts any one of the following aspects 1 to 3 and preferably the aspect 1.

Aspect 1: W^(A) represents CR^(A2), in which R^(A2) represents a single bond

Aspect 2: W^(A) represents NR^(A1), in which R^(A1) represents a single bond

Aspect 3: W^(A) represents C(R^(A2))₂, in which one R^(A2) represents a single bond and the other R^(A2) represents a hydrogen atom, a halogen atom, or the alkyl group.

In each of the aspects, CR^(A2) (carbon atom), NR^(A1) (nitrogen atom), or C(R^(A2))₂ (carbon atom) including a single bond represents a binding site (in the formula, represented by *) in Formula (A-6).

The aromatic heterocyclic groups represented by Formula (A-7) and Formula (A-12) each independently may have a substituent. The substituent is not particularly limited and has the same definition and the same preferable ranges as the substituent which may be included in the aromatic hydrocarbon group and the aromatic heterocyclic group which may be used as A¹⁰.

A¹² represents preferably an aromatic heterocyclic group represented by any one or Formulae (A-1) to (A-6), (A-8) to (A-10), and (A-12) among the Formulae (A-1) to (A-12), more preferably an aromatic heterocyclic group represented by Formula (A-1), Formula (A-3), Formula (A-4), or Formula (A-6), and still more preferably an aromatic heterocyclic group represented by Formula (A-3).

The group represented by the following Formula (1-1) will be described.

In Formula (1-1), L_(a) represents an alkylene group having 1 to 20 carbon atoms which may have at least one of —O—, —S—, or —NR^(1S)— in a carbon chain.

In the present invention, examples of the alkylene group having —O— in a carbon chain include a group having —O— in the middle of a carbon-carbon bond, a group having —O— at one terminal or both terminals of a carbon-carbon bond, and a group having —O— in the middle of and at one terminal or both terminals of a carbon-carbon bond. The same shall be applied to the alkylene group having —S— or —NR^(1S)— in a carbon chain. In addition, in a ease where the alkylene group has —O—, —S—, and —NR^(s)—, the total number of these groups is at least one, and the upper limit thereof is not particularly limited and is, for example, 5.

The alkylene group which may be used as L_(a) may be linear, branched, or cyclic and is preferably a linear or branched alkylene group. From the viewpoints of carrier mobility and solubility, the number of carbon atoms in the alkylene group is preferably 1 to 15 and more preferably 1 to 10.

In a case where the alkylene group which may be used as L_(a) is branched, the number of carbon atoms in the branch portion is included in the number of carbon atoms in the alkylene group represented by L_(a). In a case where L_(a) represents —NR^(1S)— in which R^(1S) has a carbon atom, the number of carbon atoms in R^(1S) is not included in the number of carbon atoms in the alkylene group which may be used as L_(a).

Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

The aromatic heterocyclic group which may be used as Ar may be a monocyclic group or a fused ring group composed of 2 or more rings. From the viewpoints of carrier mobility, it is preferable that the aromatic hydrocarbon group is a monocyclic group. In a case where the aromatic heterocyclic group is a monocyclic group, it is preferable that the number of ring members is 5 to 7. In addition, as the ring-constituting heteroatom included in the aromatic heterocyclic group, a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom is preferable, and a sulfur atom is more preferable.

As the aromatic heterocyclic group which may be used as Ar, an aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) is preferable among the aromatic heterocyclic groups which may be used as A¹⁰.

The aromatic hydrocarbon group having 6 to 18 carbon atoms which may be used as Ar is not particularly limited, and examples thereof include a benzene ring group, a naphthalene ring group, and a group obtained by removing two or more hydrogen atoms from an aromatic hydrocarbon (for example, a fluorene ring) in which three or more rings are fused. Among these, from the viewpoint of carrier mobility, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.

L_(b) represents an alkyl group having 1 to 100 carbon atoms which may have at least one of —O—, —S—, or —NR^(2S)— in a carbon chain.

The alkyl group which may be used as L_(b) may be linear, branched, or cyclic. From the viewpoints of carrier mobility and solubility, a linear or branched alkyl group is preferable, and a branched alkyl group is more preferable. In addition, the alkyl group may be an alkyl halide group having a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom and more preferably a fluorine atom) as a substituent.

The number of carbon atoms in the alkyl group which may be used as L_(b) is 1 to 100 and preferably 9 to 100.

In addition, in a case where the group represented by Formula (1-1) has a plurality of L_(b)'s, from the viewpoints of carrier mobility and solubility, at least one L_(b) represents preferably the alkyl group having 9 to 100 carbon atoms, more preferably the alkyl group having 20 to 100 carbon atoms, and still more preferably the alkyl group having 20 to 40 carbon atoms.

In a case where the alkyl group which may be used as L_(b) is branched, the number of carbon atoms in the branch portion is included in the number of carbon atoms in the alkyl group which may be used as L_(b). In a case where L_(b) includes —NR^(2S)— in which has a carbon atom, the number of carbon atoms in R^(2S) is not included in the number of carbon atoms in the alkylene group which may be used as L_(b).

R^(1S) and R^(2S) each independently represent a hydrogen atom or a substituent. The substituent which may be used as R^(1S) and R^(2S) is not particularly limited, and examples thereof include an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). In particular, R^(1S) and R^(2S) each independently represent preferably a hydrogen atom or an alkyl group and more preferably an alkyl group.

The position of Ar (ring-constituting atom) to which L_(b) is bonded is not particularly limited. For example, it is preferable that Ar is in the 2-position to 4-position with respect to L_(a) (the ring-constituting atom to which L_(a) is bonded is in the 1-position), and it is more preferable that at least one L_(b) is bonded to the 4-position.

1 represents an integer of 1 to 5 and preferably 1 or 2. In a case where l represents an integer of 2 or more, a plurality of L_(b)'s may be the same as or different from each other.

In Formula (1-1), * represents a binding site for introduction to the repeating unit. In this binding site, L_(a) as the group represented by Formula (1-1) is bonded to the group derived from die dinaphtho chalcogenophene compound, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a vinylene group which may be used as A¹⁰, a ring-constituting nitrogen atom in Formula (A-1) or (A-2), a nitrogen atom in NR^(X) of X^(A), a nitrogen atom in NR^(A1) of W^(A), or an aromatic hydrocarbon group or an aromatic heterocyclic group represented by A¹¹ or A¹³ described below.

Examples of the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) will be shown below and in Examples, but the present invention is not limited to these examples. In the following aromatic heterocyclic groups, R^(N), R^(X), and * are as described above.

in Formula (2), m¹² represents an integer of 0 to 4, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 or 2, and even still more preferably 1.

In a case where m¹² represents an integer of 2 to 4, a plurality of A¹²'s may represent the same aromatic heterocyclic group or different aromatic heterocyclic groups.

A¹¹ and A¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group other than aromatic heterocyclic groups represented by Formulae (A-1) to (A-12), a vinylene group, or an ethynylene group.

The aromatic hydrocarbon group and the vinylene group which may be used as A¹¹ and A¹³ are not particularly limited and have the same definitions and the same preferable ranges as the aromatic hydrocarbon group and the vinylene group which may be used as A¹⁰.

The aromatic heterocyclic group which may be used as A¹¹ and A¹³ is not particularly limited as long as it is an aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12), and may be a monocyclic group or a fused ring group composed of 2 or more rings. In addition, the aromatic heterocyclic group may be a group in which monocyclic or fused heterocyclic groups are linked through a carbon-carbon double bond. In a case where the aromatic heterocyclic group is a monocyclic group, it is preferable that the number of ring members is 5 to 7. In addition, as the ring-constituting heteroatom included in the aromatic heterocyclic group, a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom is preferable, and a sulfur atom is more preferable.

The aromatic heterocyclic group which may be used as A¹¹ and A¹³ has the same definition and the same preferable ranges as the aromatic heterocyclic group other than the aromatic heterocyclic groups represented by Formulae (A-1) to (A-12) among the aromatic heterocyclic groups which may be used as A¹⁰.

A¹¹ and A¹³ each independently represent preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, more preferably a benzene ring or an aromatic heterocyclic group, still more preferably a benzene ring or a group represented by Formula (Ar-1) shown below, even still more preferably a benzene ring, a furan ring, a thiophene ring, or a selenophene ring, and most preferably a thiophene ring.

A¹¹ and A¹³ may be the same as or different from each other.

A¹¹ and A¹³ each independently may have a substituent. The substituent is not particularly limited and has the same definition and the same preferable ranges as the substituent which may be included in the aromatic hydrocarbon group and the aromatic heterocyclic group which may be used as A¹⁰.

In Formula (2), it is preferable that -(A¹¹)m¹¹- and -(A¹³)m¹³- are each independently represented by the following Formula (Ar-1), and it is more preferable that A¹² represents an aromatic heterocyclic groups represented by the following Formulae (A-1) to (A-12) and both and -(A¹¹)m¹¹- and -(A¹³)m¹³ are represented by the following Formula (Ar-1).

In Formula (Ar-1), * represents a binding site to another group forming the repeating unit represented by Formula (2).

X^(d) represents an oxygen atom, a sulfur atom, a selenium atom, or NR^(D1), X^(d) represents preferably an oxygen atom, a sulfur atom, or a selenium atom, more preferably an oxygen atom or a sulfur atom, and still more preferably a sulfur atom.

Z^(d)'s each independently represent a nitrogen atom or CR^(D2). In the ring represented by the above formula, an aspect in which one of the two Z^(d)'s represents a nitrogen atom and the other one of the two Z^(d)'s represents CR^(D2) or an aspect in which the two Z^(d)'s represent CR^(D2) is preferable, and an aspect in which the two Z^(d)'s represent CRD² is more preferable.

R^(D1) and R^(D2) each independently represent a hydrogen atom or a substituent and preferably a hydrogen atom. The substituent which may be used as R^(D1) and R^(D2) is not particularly limited and has the same definition and the same preferable ranges as the substituent which may be included in the aromatic hydrocarbon group and the aromatic heterocyclic group which may be used as A¹⁰.

In a case where R^(D1) and R^(D2) each independently represent an alkoxy group, R^(D1) and R^(D2) are bonded to each other to form an alkylenedioxy group, and an alkylenedioxythiophene ring may be formed as a ring represented by Formula (Ar-1). The number of carbon atoms in the alkylene group is as described above and is preferably 1 to 3.

In Formula (Ar-1), an aspect in which X^(d) represents a sulfur atom and all the Z^(d)'s represent CR^(D2) (R^(D2) represent preferably a hydrogen atom) is preferable.

In Formula (Ar-1), in a case where all the Z^(d)'s represent CR^(D2) and R^(D2) represents a substituent, two R^(D2)'s may be bonded to each other to form a ring.

In Formula (Ar-1), m^(d) represents an integer of 1 to 4 and preferably 1 or 2.

In Formula (2), m¹¹ and each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 1 or 2.

In a case where m¹¹ and m¹³ each independently represent an integer of 2 to 4, a plurality of A¹¹'s and a plurality of A¹³'s may be the same as or different from each other.

In Formula (2), m¹¹ to m¹³ may each independently represent 0. However, it is preferable that all the m¹¹ to m¹³ do not represent 0, that is, the sum of m¹¹, m¹², and m¹³ is 1 or more. Specifically, the sum of m¹¹, m¹², and m¹³ is preferably 1 to 12.

In the repeating unit represented by Formula (2), in a case where m¹² represents 0, a group (a group corresponding to A¹¹ and A¹³) other than the group derived from the dinaphtho chalcogenophene compound in the repeating unit preferentially belongs to A¹¹. For example, it is considered that m¹¹ represents 4 and m¹³ represents 0 in a polymer 2 used in Examples.

Specific examples of the repeating unit represented by Formula (1) will be shown below and in Examples, but the present invention is not limited thereto.

In the following specific examples, examples including a dinaphthothiophene skeleton are shown. However, in the present invention, examples including a dinaphthofuran skeleton or a dinaphthoselenophene skeleton instead of the dinaphthothiophene skeleton may also be used.

In addition, in each of the following specific examples, at least one hydrogen atom may be substituted with, for example, an alkyl group which may have at least one of —O—, —S—, or —NR— or the group represented by Formula (1-1). The alkyl group has the same definition as the alkyl group as a preferable substituent which may be used as R¹¹ and R¹². R represents a hydrogen atom or a substituent, and the substituent which may be used as R has the same definition as the substituent of R^(1S) and R^(2S).

The polymer according to the embodiment of the present invention may include one repeating unit represented by Formula (1) or two or more repeating units represented by Formula (1).

The polymer according to the embodiment of the present invention includes two or more repeating units represented by Formula (1). The polymer including two or more repeating units may be a random copolymer or a block copolymer. The polymer according to the embodiment of the present invention may be an oligomer in which the number of repeating units (polymerization degree) n is 2 to 9, or a polymer compound (polymer) in which the number of repeating units (polymerization degree) n is 10 or more. In particular, it is preferable that the polymer according to the embodiment of the present invention is a polymer compound from the viewpoint of simultaneously obtaining high carrier mobility, uniformity thereof, and high heat resistance.

The polymerization degree n can be calculated based on a weight-average molecular weight described below and the mass of each of the repeating units.

The polymer according to the embodiment of the present invention may include a repeating unit (referred to as “the other repeating unit”) other than the repeating unit represented by Formula (1). In the polymer according to the embodiment of the present invention, the other repeating unit may be present at a main chain thereof, or may be present between the group derived from the dinaphtho chalcogenophene compound and A¹⁰ in the repeating unit represented by Formula (1).

In the polymer according to the embodiment of the present invention, the content of the repeating unit represented by Formula (1) is preferably 60% to 100%, more preferably 80% to 100%, and still more preferably 90% to 100% with respect to the total mol number of all the repeating units in the polymer according to the embodiment of the present invention. It is even still more preferable that the polymer according to the embodiment of the present invention substantially consists of only the repeating unit represented by Formula (1). “Substantially consisting of only the repeating unit represented by Formula (1)” represents that the molar ratio of the repeating unit represented by Formula (1) in the polymer is 95% or higher, preferably 97% or higher, and more preferably 99% or higher.

In a case where the content of the repeating unit represented by Formula (1) is in the above-described range, an organic semiconductor film having a higher carrier mobility, a small variation in carrier mobility, and higher heat resistance can be obtained.

From the viewpoints of improving carrier mobility and preventing a variation, the weight-average molecular weight of the polymer according to the embodiment of the present invention is preferably 2000 or higher, more preferably 10000 or higher, still more preferably 2000or higher, even still more preferably 30000 or higher, and most preferably 45000 or higher. In addition, from the viewpoints of solubility, the weight-average molecular weight is preferably 1000000 or lower, more preferably 300000 or lower, still more preferably 200000 or lower, and even still more preferably 150000 or lower.

In the present invention, the weight-average molecular weight and the number-average molecular weight are measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, for example, HLC-8121GPC (manufactured by Tosoh Corporation) is used as a GPC, two columns GMH_(HR)-H (20) HT (manufactured by Tosoh. Corporation, 7.8 mm ID×30 cm) are used as columns, and 1,2,4-trichlorohenzene is used as an eluent. In addition, the measurement can be used using an infrared (IR) detector under conditions of sample concentration: 0.02 mass %, flow rate: 1.0 mL/min, sample injection volume: 300 μL, and measurement temperature: 160° C. In addition, a calibration curve can be obtained from 12 samples of “Standard samples, TSK standard, polystyrene”: “F-128”, “F-80”, “F-40”, “F-20”, “F-10”, “F-4”, “F-2”, “F-1”, “A-5000”, “A-2500”, “A-1000”, and “A-500” (manufactured by Tosoh Corporation).

A terminal structure of the polymer according to the embodiment of the present invention is not particularly limited and is not uniquely determined depending on whether or not the other repeating unit is present, the kind of a base material used for the synthesis, or the kind of a quenching agent (reaction terminator) used for the synthesis. Examples of the terminal structure include a hydrogen atom, a hydroxy group, a halogen atom, an ethylenically unsaturated group, an alkyl group, an aromatic heterocyclic group (preferably a, thiophene ring), and an aromatic hydrocarbon group (preferably a benzene ring).

A synthesis method of the polymer according to the embodiment of the present invention is not particularly limited, and the polymer according to the embodiment of the present invention can be synthesized using a typical method. For example, respective precursor compounds with which the group derived from the dinaphtho chalcogenophenc compound in Formula (1) and the respective groups represented by A¹⁰ can be introduced are synthesized, and the respective precursors are caused to undergo a cross-coupling reaction such as a Suzuki coupling reaction or a Stille coupling reaction. As a result, the polymer can be synthesized. The synthesis of the polymer according to the embodiment of the present invention can be referred to, for example, JP2010-527327A, JP2007-516315A, JP2014-515043A, JP2014-507488A, JP2011-501451A, JP2010-18790A, WO2012/174561A, JP2011-514399A, and JP2011-514913A.

[Organic Semiconductor Composition]

Next, an organic semiconductor composition according to the embodiment of the present invention will be described.

The organic semiconductor composition includes the above-described polymer and a solvent, and is preferably used for forming an organic semiconductor film according to the embodiment of the present invention.

<Polymer>

As described above, one polymer may be used alone, or two or more polymers may be used in combination.

The content of the polymer in the organic semiconductor composition is not particularly limited and can be expressed as, for example, the content in solid matter excluding the solvent described below. It is preferable that the content in the solid matter is in the same range as the content of the polymer in the organic semiconductor film described below.

<Solvent>

The solvent is not particularly limited as long as the above-described polymer is soluble or dispersible therein, and examples thereof include an inorganic solvent and an organic solvent. Among these, an organic solvent is preferable. As the solvent, one kind may be used alone, or two or more kinds may be used in combination.

The organic solvent is not particularly limited, and examples thereof include: an (aliphatic) hydrocarbon solvent such as hexane, octane, or decane; an aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, ethylbenzene, decaline, 1-methylnaphthalene, tetralin, or anisole; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; a halogenated hydrocarbon solvent such as dichloromethane, chloroform, tetrachloromethane, dichioroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, or chlorotoluene; an ester solvent such as ethyl acetate, butyl acetate, amyl acetate, or ethyl lactate; an alcohol solvent such as methanol, propanol, butanol, pentanol hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, or ethylene glycol; an ether solvent such as butoxybenzene, dibutyl ether, tetrahydrofuran, or dioxane; an amide solvent such as N,N-dimethylformamide or N,N-dimethylacetamide; an imide solvent such as 1-methyl-2-pyrrolidone or 1-methyl-2-imidazolidinone; a sulfoxide solvent such as dimethyl sulfoxide; and a nitrile solvent such as acetonitrile.

The content of the solvent in the organic semiconductor composition is preferably 90 to 99.99 mass %, more preferably 95 to 99.99 mass %, and still more preferably 96 to 99.95 mass %.

<Other Components>

The organic semiconductor composition according to the embodiment of the present invention may tither include components other than the polymer according to the embodiment of the present invention and the solvent.

Examples of the components include a hinder polymer and various additives.

(Binder Polymer)

As the binder polymer, any binder polymer can be used without any particular limitation to hinder polymers which are typically used in an organic semiconductor composition.

Examples of the binder polymer include: an insulating polymer such as polystyrene, poly(α-methyl styrene), polyvinyl cinnamate, poly(4-divinylbenzene), poly(4-vinyl phenol), poly(4-methyl styrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, or polypropylene and a copolymer thereof; a semiconductor polymer such as polysilane, polycarbazole, polyarylamine, polyfluorene, polythiophene, polypyrrole, polyaniline, polyparaphenylene vinylene, polyacene, polyheteroacene, and a copolymer thereof; rubber; and a thermoplastic elastomer.

In particular, as the binder polymer, a polymer compound having a benzene ring (a polymer which includes a repeating unit having a benzene ring group) is preferable. The content of the repeating unit having a benzene ring group is not particularly limited and is preferably 50 mol % or higher, more preferably 70 mol % or higher, and still more preferably 90 mol %, or higher with respect to all the repeating units. The upper limit is not particularly limited and, for example, 100 mol %.

The weight-average molecular weight of the binder polymer is not particularly limited and is preferably 1000 to 10000000, more preferably 3000 to 5000000, and still more preferably 5000 to 3000000.

The content of the binder polymer in the organic semiconductor composition is not particularly limited. For example, the content in the solid matter is preferably in the same range as the content of the binder polymer in the organic semiconductor film described below. In a case where an organic semiconductor element, in particular, an organic semiconductor film of an organic thin film transistor element is formed using the organic semiconductor composition in which the content of the binder polymer is in the above-described range, the carrier mobility and heat resistance are further improved.

(Additives)

As the additives, any additives can be used without any particular limitation to additives which are typically used in an organic semiconductor composition.

The content of the additives in the organic semiconductor composition is not particularly limited. For example, the content in the solid matter is preferably in the same range as the content of the additives in the organic semiconductor film described below. In a ease where the content of the additives is in the above-described range, film forming properties are excellent. For example, in a ease where an organic semiconductor element, in particular, an organic semiconductor film of an organic thin film transistor element is formed using the organic semiconductor composition in which the content of the additives is in the above-described range, film forming properties are excellent, and the carrier mobility and heat resistance are further improved.

<Preparation Method>

A preparation method of the organic semiconductor composition is not particularly limited, and a typical preparation method can be adopted. For example, the organic semiconductor composition according to the embodiment of the present invention can be prepared by adding predetermined amounts of the respective components to the solvent and appropriately stirring the components.

[Organic Semiconductor Element]

Next, an organic semiconductor element according to the embodiment of the present invention will be described.

The organic semiconductor element according to the embodiment of the present invention includes the organic semiconductor film according to the embodiment of the present invention.

The organic semiconductor element according to the embodiment of the present invention is not particularly limited and is preferably used as a non-light-emitting organic semiconductor device. The non-light-emitting organic semiconductor device is not particularly limited as long as it is a device that does not emit light, and examples thereof include an organic thin film transistor element that controls a current amount or a voltage amount, an organic photoelectric conversion element (for example, a solid image pickup element for an optical sense or a solar cell for energy conversion) that converts light energy into electric power, an organic thermoelectric conversion element that converts thermal energy into electric power, a gas sensor, an organic rectifying element, an organic inverter, and an information recording element. In the non-light-emitting organic semiconductor device, it is preferable that the organic semiconductor film functions as an electronic element.

<Organic Thin Film Transistor Element>

An organic thin film transistor element as a preferable aspect of the organic semiconductor element according to the embodiment of the present invention will be described.

The organic thin film transistor element (also referred to as “organic TFT element”) according to the embodiment of the present invention includes the organic semiconductor film according to the embodiment of the present invention (also referred to as “organic semiconductor layer” or “semiconductor active layer”) and may further include a source electrode, a dram electrode, and a gate electrode.

The organic TFT element according to the embodiment of the present invention includes, on a substrate, a gate electrode, an organic semiconductor layer, a gate insulating layer that is provided between the gate electrode and the organic semiconductor layer, and a source electrode and a drain electrode that are provided adjacent to the organic semiconductor layer and are linked to each other through the organic semiconductor layer. In the organic TFT element, the organic semiconductor layer and the gate insulating layer are provided adjacent to each other.

A structure of the organic thin film transistor element according to the embodiment of the present invention is not particularly limited as long as it includes the respective layers. For example, any structure such as a bottom contact type (a bottom gate-bottom contact type and a top gate-bottom contact type) or a top contact type (a bottom gate-top contact type and a top gate-top contact type) may be adopted. It is more preferable that the organic thin film transistor element according to the embodiment of the present invention is a bottom gate-bottom contact type or bottom gate-top contact type (collectively referred to as “bottom gate type”).

Hereinafter, an example of the organic thin film transistor element according to the embodiment of the present invention will be described with reference to the accompanying drawings.

—Bottom Gate-Bottom Contact type Organic Thin Film Transistor Element—

FIG. 1 is a schematic cross-sectional view showing a bottom gate-bottom contact type organic thin film transistor element 100 as an example of the semiconductor element according to the embodiment of the present invention.

As shown in FIG. 1 the organic thin film transistor element 100 includes a substrate (base material) 10, a gate electrode 20, a gate insulating film 30, a source electrode 40 and a drain electrode 42, an organic semiconductor film 50, and a sealing layer 60 in this order.

Hereinafter, the substrate (base material), the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer, and preparation methods thereof will be described in detail.

(Substrate)

The substrate functions to support the gate electrode, the source electrode, the drain electrode, and the like described below.

The kind of the substrate is not particularly limited, and examples thereof include a plastic substrate, a silicon substrate, a glass substrate, and a ceramic substrate. In particular, from the viewpoints of applicability to each device and costs, a glass substrate or a plastic substrate is preferable.

The thickness of the substrate is not particularly limited and is, for example, preferably 10 mm or less, more preferably 2 mm or less, and still more preferably 1.5 mm or less. On the other hand, the thickness of the substrate is preferably 0.01 mm or more and more preferably 0.05 mm or more.

(Gate Electrode)

As the gate electrode, a typical electrode that is used as a gate electrode of an organic TFT element can be used without any particular limitation.

A material (electrode material) which forms the gate electrode is not particularly limited, and examples thereof include: a metal such as gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, or sodium; a conductive oxide such as InO₂, Sn₂, or indium tin oxide (ITO); a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polydiacetylene; a semiconductor such as silicon, germanium, or gallium-arsenic; and a carbon material such as fulterene, carbon nanotube, or graphite. Among these, the metal is preferable, and silver or aluminum is more preferable.

The thickness of the gate electrode is not particularly limited and is preferably 20 to 200 nm.

The gate electrode may function as the substrate. In this case, the substrate is not necessarily provided.

A method of forming the gate electrode is not particularly limited, and examples thereof include a method of performing vacuum deposition (hereinafter, simply referred to as “deposition”) or sputtering on the substrate using the above-described electrode material and a method of applying or printing an electrode-forming composition including the above-described electrode material. In addition, in a case where an electrode is patterned, examples of a patterning method include a printing method such as ink jet priming, screen printing, offset printing, or relief printing (flexographic printing); a photolithography method, and a mask deposition method.

(Gate Insulating Layer)

The gate insulating film is not particularly limited as long as it is an insulating film (layer) and may have a single-layer structure or a multi-layer structure.

It is preferable that the gate insulating layer is formed of an insulating material, and preferable examples of the insulating material include an organic polymer and an inorganic oxide.

The organic polymer, the inorganic oxide, or the like is not particularly limited as long as it has insulating characteristics, and an organic polymer or an inorganic oxide with which a thin film, for example, a thin film having a thickness of 1 μm or less can be formed is preferable.

As the organic polymer or the inorganic oxide, one kind may be used alone, and two or more kinds may be used in combination. In addition, an organic polymer or an inorganic oxide may be used in combination.

The organic polymer is not particularly limited, and examples thereof include: a poly(methlacrylate such as polyvinyl phenol, polystyrene (PS), or polymethyl methacrylate; a cyclic fluoroalkyl polymer such as polyvinyl alcohol, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), or CYTOP (registered trade name); a polyorganosiloxane such as polycycloolefin, polyester, polyethersulfone, polyether ketone, polyimide, an epoxy resin, or polydimethylsiloxane (PDMS); polysilsesquioxane; and butadiene rubber. In addition to the above-described examples, a thermosetting resin such as a phenolic resin, a novolac resin, a cinnamate resin, an acrylic resin, or a polyparaxylylene resin may also be used.

The organic polymer can also be used in combination with a compound having a reactive substituent such as an alkoxysilyl group, a vinyl group, an acryloyloxy group, an epoxy group, or a methylol group.

In a case where the gate insulating layer is formed of the organic polymer, it is preferable that the organic polymer is crosslinked and cured, for example, in order to improve solvent resistance or insulation resistance of the gate insulating layer. It is preferable that crosslinking is performed by generating an acid or a radical using either or both light and heat.

In a case where the organic polymer is crosslinked by a radical, as a radical generator that generates a radical using light or heat, for example, a thermal polymerization initiator (H1) and a photopolymerization initiator (H2) described in paragraphs “0182” to “0186” of JP2013-214649A, a photoradical generator described in paragraphs “0046” to “0051” of JP2011-186069A, or a photoradical polymerization initiator described in paragraphs “0042” to “0056” of JP2010-285518A can be preferably used, the contents of which are preferably incorporated herein by reference.

In addition, “a compound (G) having a number-average molecular weight (Mn) of 140 to 5000, having a crosslinking functional group, and not having a fluorine atom” which is described in paragraphs “0167” to “0177” of JP2013-214649A can also be preferably used, the contents of which are incorporated herein by reference.

In a case where the organic polymer is crosslinked by an acid, as a photoacid generator that generates an acid using light, for example, a photocationic polymerization initiator described in paragraphs “0033” and “0034” of JP2010-285518A or an acid generator, in particular, a sulfonium salt or an iodonium salt described in paragraphs “0120” to “0136” of JP2012-163946A can be preferably used, the contents of which are preferably incorporated herein by reference.

As a thermal acid generator (catalyst) that generates an acid using heat, for example, a thermal cationic polymerization initiator, in particular, an onium salt described in paragraphs “0035” to “0038” of JP2010-285518A or a catalyst, in particular, a sulfonic acid or a sulfonic acid amine salt described in paragraphs “0034” and “0035” of JP2005-354012A can be preferably used, the contents of which are preferably incorporated herein by reference.

In addition, a crosslinking agent, in particular, a bifunctional or higher epoxy compound or oxetane compound described in paragraphs “0032” and “0033” of JP2005-354012A, a crosslinking agent, in particular, a compound having two or more crosslinking groups at least one of which is a methylol group or an NH group described in paragraphs “0046” to “0062” of JP2006-303465A, or a compound having two or more hydroxymethyl groups or alkoxymethyl groups in a molecule described in paragraphs “0137” to “0145” of JP2012-163946A is also preferably used, the contents of which are preferably incorporated herein by reference.

A method of forming the gate insulating layer using the organic polymer is not particularly limited, and examples thereof include a method of applying a coating solution including the organic polymer and optionally curing the applied coating film.

The solvent used in the coating solution is not particularly limited as long as the organic polymer is soluble or dispersible therein, and can be appropriately selected from typically used solvents according to the kind and the like of the organic polymer.

A coating method is not particularly limited, and examples thereof include the above-described printing methods. Among these, a wet coating method such as a microgravure coating method, a dip coating method, a screen coating printing method, a die coating method, or a spin coating method is preferable.

Coating conditions are also not particularly limited and can be appropriately set.

A method and conditions for curing are not particularly limited as long as they are a method and conditions in which the organic polymer can be crosslinked. For example, the crosslinking method (radical or acid) can be appropriately set according to the kind and the like of a photoacid generator, a thermal acid generator, or the like to be used.

The inorganic oxide is not particularly limited, and examples thereof include: an oxide such as silicon oxide, silicon nitride (SiN_(y)), hafnium oxide, titanium oxide, tantalum oxide, aluminum oxide, niobium oxide, zirconium oxide, copper oxide, or nickel oxide; a compound having a perovskite structure such as SrTiO₃, CaTiO₃, BaTiO₃, MgTiO₃, or SrNb₂O₆; and a composite oxide or a mixture thereof.

Examples of the silicon oxide include silicon oxide (SiO_(x)), boron phosphorus silicon glass (BPSCi), phosphorus silicon glass (PSG), borosilicate glass (BSG) arsenic silicate glass (AsSG), lead silicate glass (PbSG), silicon nitride oxide (SiON), spin-on-glass (SOG), and a low dielectric constant SiO₂ material (for example, polyarylether, a cycloperfluorocarbon polymer, benzocyclobutene, a cyclic fluororesin, polytetrafluoroethylene, fluorinated aryl ether, fluorinated polyimide, amorphous carbon, or organic SOG).

A method of forming the gate insulating layer using the inorganic oxide is not particularly limited. For example, a vacuum film formation method such as a vacuum deposition method, a sputtering method, or an ion plating or chemical vapor deposition (CVD) method can be used. In addition, the film formation may be assisted with plasma using predetermined gas, an ion gun, or a radical gun.

In addition, the gate insulating layer can also be formed by causing a precursor corresponding to each of metal oxides, specifically, a metal halide such as a chloride or a bromide, a metal alkoxide, a metal hydroxide, or the like is to react with an acid such as hydrochloric acid, sulfuric acid, or nitric acid or a base such as sodium hydroxide or potassium hydroxide in alcohol or water for hydrolysis. In a case where the solution-based process is used, the wet coating method can be used.

In a case where the gate insulating layer is formed using the inorganic oxide, in addition to the above-described method, a combination of any one of a lift-off method, a sol-gel method, an electrodeposition method, or a shadow mask method with a patterning method can also be optionally used.

The gate insulating layer may undergo a surface treatment such as a corona treatment, a plasma treatment, or an ultraviolet (UV)/ozone treatment. In this case, it is preferable that the surface roughness is not increased due to each treatment. For example, it is preferable that an arithmetic average roughness Ra or a root-mean-square roughness R_(q) (both of which are defined according to JIS B0601:2013) of the treated gate insulating layer surface is 0.5 nm or lower.

The thickness of the gate insulating film is not particularly limited and is preferably 100 to 1000 nm.

(Source Electrode and Drain Electrode)

In the organic TFT element according to the embodiment of the present invention, the source electrode is an electrode into which a current flows from the outside through a wiring. In addition, the drain electrode is an electrode from which a current flows to the outside through a wiring.

As a material which forms the source electrode and the drain electrode, the same electrode material as that of the gate electrode can be used. Among these, a metal is preferable, and silver is more preferable.

The thickness of each of the source electrode and the drain electrode is not particularly limited and is preferably 1 nm or more and more preferably 10 nm or more. In addition, the thickness of each of the source electrode and the drain electrode is preferably 500 nm or less and more preferably 300 nm or less.

An interval (gate length) between the source electrode and the drain electrode can be appropriately determined and is, for example, preferably 200 μm or less and more preferably 100 μm or less. In addition, the gate width can be appropriately determined and is, for example, preferably 5000 μm or less and more preferably 1000 nm or less.

A method of forming the source electrode and the drain electrode is not particularly limited, and examples thereof include a method of performing vacuum deposition or sputtering using the electrode material on the substrate on which the gate electrode and the gate insulating film are formed and a method of applying or printing an electrode-forming composition to or on the substrate. In a case where the source electrode and the drain electrode are patterned, a patterning method thereof is the same as that of the gate electrode.

(Organic Semiconductor Film)

In the organic TFT element, the organic semiconductor film includes the above-described polymer according to the embodiment of the present invention. The organic semiconductor film may include one polymer or two or more polymers.

In a case where, the organic semiconductor film includes the polymer according to the embodiment of the present invention, high and uniform carrier mobility and high heat resistance can be simultaneously obtained. The reason for this is not clear but is presumed to be as follows. That is, the group derived from the dinaphtho chalcogenophene compound as the component of the polymer according to the embodiment of the present invention functions as an electron-donating unit (donor unit) and has a structure in which five rings are fused. Therefore, this structure has a relatively wide π-plane and is advantageous for intermolecular packing. Further, the polymer according to the embodiment of the present invention also has A¹⁰ as the electron-accepting unit (acceptor unit), preferably the aromatic heterocyclic group represented by any one of Formulae (A-1) to (A-12). As a result, the main chain skeleton is a so-called “D-A polymer” including the electron-donating unit (donor unit) and the electron-accepting unit (acceptor unit). The D-A polymer having the above-described specific skeleton is likely to be polymerized in a molecule, and thus is advantageous for intermolecular packing. Therefore, it is presumed that the carrier mobility is high and the heat resistance is high.

In addition, the group derived from the dinaphtho chalcogenophene compound has an asymmetrical structure, and this group itself has a dipole moment. As a result, the solubility is higher than that of a polymer having a symmetrical skeleton. Therefore, it is presumed that the coating film obtained after applying a composition including the polymer has a small unevenness and is uniform, and an organic semiconductor element having a small variation in carrier mobility can be obtained.

The content of the polymer in the organic semiconductor film is not particularly limited and can be appropriately set. For example, the content of the polymer is preferably 10 mass % or higher, more preferably 30 mass % or higher, and still more preferably 50 mass % or higher. The upper limit may be 100 mass %. In a case where the organic semiconductor film includes the binder polymer and the like, the upper limit is, for example, preferably 90 mass % or lower and more preferably 80 mass % or lower.

In addition to the polymer according to the embodiment of the present invention, the organic semiconductor film may further include the binder polymer or the additives. The binder polymer and the additives are as described above.

As each of the binder polymer and the additives, one kind may be included, or two or more kinds may be included.

The content of the binder polymer in the organic semiconductor film is not particularly limited and can be appropriately set. For example, the content of the binder is preferably 90 mass % or lower, more preferably 70 mass % or lower, and still more preferably 50 mass % or lower. The lower limit may be 0 mass % or higher and, for example, is preferably 10 mass % or higher, more preferably 15 mass % or higher, and still more preferably 20 mass % or higher.

The content of the additives in the organic semiconductor film is preferably 10 mass % or lower, more preferably 5 massy or lower, and still more preferably 1 mass % or lower.

The thickness of the organic semiconductor film cannot be uniquely determined according to the organic semiconductor element and is, for example, preferably 10 to 500 nm and more preferably 20 to 200 nm.

The organic semiconductor film can. be formed by applying the above-described organic semiconductor composition. Specifically, the organic semiconductor film can be formed by applying the above-described organic semiconductor composition to the substrate and drying the applied organic semiconductor composition.

In the present invention, the application of the organic semiconductor composition to the substrate includes an aspect in which the organic semiconductor composition is directly applied to the substrate and an aspect in which the organic semiconductor composition is applied over the substrate through another layer provided on the substrate. The other layer (a layer that is provided adjacent to the organic semiconductor layer and functions as a base of the organic semiconductor layer) to which the organic semiconductor composition is applied is necessarily determined according to the structure of the organic thin film transistor. For example, in the case of a bottom gate type, the other layer is the gate insulating film, and in the case of a top gate type (a top gate-bottom contact type or a top gate-top contact type), the other layer is the source electrode or the drain electrode.

As a coating method of the organic semiconductor composition, a typical method can be used, and examples thereof include a bar coating method, a spin coating method, a knife coating method, a doctor blade method, an ink jet printing method, a flexographic printing method, a gravure printing method, and a screen printing method. Further, as the coating method of the organic semiconductor composition, for example, a method (so-called gap casting method) of forming an organic semiconductor film described in JP2013-207085A or a method (so-called edge casting method or continuous edge casting method) of forming an organic semiconductor thin film described in WO2014/175351A can be preferably used.

For drying (drying treatment), appropriate conditions can be selected according to the kind of each of the components included in the organic semiconductor composition. Natural drying may be performed, but heating is preferable from the viewpoint of improving productivity. Heating conditions cannot be uniquely determined. For example, the heating temperature is preferably 30° C. to 250° C., more preferably 40° C. to 200° C., and still more preferably 50° C. to 150° C., and the heating time is preferably 10 to 300 minutes and more preferably 20 to 180 minutes.

(Sealing Layer)

The organic semiconductor film according to the embodiment of the present invention includes the polymer according to the embodiment of the present invention as described above and exhibits high heat resistance. Accordingly, even in a case where a heating step such as the formation of the sealing layer or the like is performed after providing the organic semiconductor, a high carrier mobility of the organic semiconductor film can be maintained.

Accordingly, in the organic thin film transistor element according to the embodiment of the present invention, it is preferable that the sealing layer is provided on the outermost layer from the viewpoint of durability. As a result, a high carrier mobility and durability can be simultaneously obtained.

For the sealing layer, a sealing agent (sealing layer-forming composition) that is typically used in the organic TFT element can be used.

It is preferable that the sealing agent is heated and dried to form the sealing layer. At this time, heating conditions cannot be uniquely determined according to the kind and the like of the sealing agent. For example, the heating temperature is preferably 50° C. to 200° C. and more preferably 100° C. to 175° C. Other conditions such as the heating time are appropriately determined according to the kind and the like of the sealing agent.

The thickness of the sealing layer is not particularly limited and is preferably 0.2 to 10 μm.

—Bottom Gate-Top Contact type Organic Thin Film Transistor Element—

FIG. 2 is a schematic cross-sectional view showing a bottom gate-top contact type organic thin film transistor element 200 as an example of the semiconductor element according to the embodiment of the present invention.

As shown in FIG. 2, the organic thin film transistor element 200 includes the substrate 10, the gate electrode 20, the gate insulating film 30, the organic semiconductor film 50, the source electrode 40 and the drain electrode 42, and the sealing layer 60 in this order.

The organic thin film transistor element 200 is the same as the organic thin film transistor element 100 except for the layer configuration (stack aspect). Accordingly, the details of the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are the same as those of the bottom gate-bottom contact type organic thin film transistor element, and thus the description thereof will not be repeated.

The organic thin film transistor element 200 includes the organic semiconductor film according to the embodiment of the present invention. Accordingly, even in a case where the source electrode and the drain electrode are formed on the organic semiconductor film by applying or printing the electrode-forming composition and then heating the applied electrode-forming composition, the high carrier mobility of the organic semiconductor film can be maintained.

EXAMPLES

The present invention will be described in more detail using Examples, but the present invention is not limited to the following Examples.

SYNTHESIS EXAMPLES

Polymers 1 to 21 used in respective examples will be described below.

The weight-average molecular weights of the respective polymers are measured using the above-described method, and the results thereof are shown in Table 1. Molecular weights of comparative compound 1 and 2 were calculated from molecular formulae, and the calculated values are shown in Table 1.

Synthesis Example 1 Synthesis of Polymer 2

An intermediate 5 and an intermediate 10 were synthesized according to the following scheme.

Abbreviations in the following scheme are as follows.

Ni(dppp)Cl₂ represents dichloro(1,3-bis(diphenylphosphino)propane)nickel (II), THF represents tetrahydrofuran, NBS represents N-bromosuceinimide, AcOH represents acetic acid. Et₂O represents diethyl ether, BuLi represents butyllithium, TMS represents trimethylsilyl, TBAF represents tetrabutylammonium fluoride, Me represents methyl, DMF represents N,N-dimethylformainide, and Tf₂O represents trifluoromethanesulfonic anhydride.

—Synthesis of Intermediate 5—

An intermediate 2 was synthesized using a method described in Macromolecules, 2010, 43, p. 9779 to 9786. Intermediates 3 and 5 were synthesized using a method described in Journal of the American Chemical Society, 2013, 135, p. 844 to 854. An intermediate 4 was synthesized using a method described in Angewandte Chemie International Edition, 1995, 34, p. 303 to 307.

—Synthesis of Intermediate 6—

1-bromo-4-methoxy-2-(trimethylsilyl ethynyl)benzene (10.5 g, 37.2 mmol) and tetrahydrofuran (75 mL) were mixed with each other in a nitrogen atmosphere and were cooled to −78° C., A 1.6 M (mol/L) normal butyllithium hexane solution (24 mL, 38.4 mmol) was added to the reaction solution and was stirred at −78° C. for 30 minutes. Next, a 0.5 M zinc chloride tehahydrafuran (THF) solution (75 mL, 37.5 mmol) was added dropwise and was stirred for 30 minutes. The reaction solution was heated to roam temperature (about 20° C.), 2,5-dibromothiophene (3 g, 12.4 mmol) and bis(triphenylphosphine)palladium (II) dichloride (870 mg, 1.24 mmol) were added thereto, and the reaction solution was heated to reflux for 12 hours. The reaction solution was cooled to room temperature and then was filtered through silica gel and concentrated. The crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=95/5). As a result, an intermediate 6 (2.9 g, yield: 48%) was obtained.

—Synthesis of Intermediate 7—

The intermediate 6 (2.0 g, 4.1 mmol) and an 1.0 M tetra butylammonium fluoride tetrahydrofuran solution (12 mL, 12.0 mmol) were mixed with each other, and the reaction solution was stirred in a nitrogen atmosphere at room temperature for 1 hour. Next, water was added to quench the reaction, and a reaction product was extracted with chloroform. The organic phase was cleaned with water, was dried using sodium sulfate, was filtered through silica gel, and was concentrated. As a result, an intermediate 7 (1.25 g, 89%) was obtained. The intermediate 7 was used for the next reaction without being purified.

An intermediate 8 was synthesized using a method described in Chemistry Letters, 2011, 40, p. 300 to 302.

—Synthesis of Intermediate 9—

The intermediate 8 (800 mg, 2.3 mmol) and chloroform (23 mL) were mixed with each other, and the mixed solution was cooled to 0° C. in a nitrogen atmosphere. A 1.0 M boron tribromide dichloromethane solution (12 mL, 12 mmol) was added dropwise to the reaction solution. The reaction solution was heated to room temperature and was stirred for 3 hours, water was added to quench the reaction, and the reaction product was extracted with ethyl acetate. The organic phase was cleaned with water, was dried using sodium sulfate, was filtered, and was concentrated. As a result, an intermediate 9 (690 mg, 95%) was obtained. The intermediate 9 was used for the next reaction without being purified.

—Synthesis of Intermediate 10—

The intermediate 9 (690 mg, 2.2 mmol) and pyridine (11 mL) were added, the reaction solution was cooled to 0° C. in a nitrogen atmosphere, and trifluoromethanesulfonic anhydride (0.8 mL, 4.8 mmol) was added dropwise. The mixed solution was heated to room temperature and then was stirred for 3 hours, and water (50 mL) was added to quench the reaction. Produced powder was separated by filtration, was dissolved in toluene, was filtered through silica gel, and was concentrated. The obtained crude product was recrystallized by toluene/methanol. As a result, an intermediate 10 (720 mg, 57%) was obtained.

A polymer 2 was synthesized using the following scheme.

The intermediate 5 (206 mg, 155 μmol), the intermediate 10 (90 mg, 155 μmol), tri(o-tolyl)phosphine (P(o-tolyl)₃: 3.8 mg, 12.4 μmol), tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃: 3.1 mg, 3.1 μmol), and dehydrated chlorobenzene (5 mL) were mixed with each other and stirred in a nitrogen atmosphere at 130° C. for 24 hours. The reaction solution was cooled to room temperature, was poured into a methanol (40 mL)/concentrated hydrochloric acid (2 mL) mixed solution, and was stirred for 2 hours. Precipitates were separated by filtration and were cleaned with methanol. The obtained crude product was sequentially Soxhlet-extracted with methanol, acetone, and hexane and soluble impurities were removed. Next, the reaction product was Soxhlet-extracted with chloroform, the obtained solution was concentrated under a reduced pressure, and methanol was added thereto. Precipitated solids were separated by filtration, were cleaned with methanol, and were dried in a vacuum at 80° C. for 12 hours. As a result, a polymer 2 (145 mg) was obtained.

In the polymer 2, the number-average molecular weight in terms of polystyrene was 1.9×10⁴, and the weight-average molecular weight was 4.6×10⁴.

Synthesis Example 2 Synthesis of Polymer 9

A polymer 9 was synthesized using the following scheme.

An intermediate 11 was a compound described in Journal of Materials Chemistry C, 2015, 3, p. 9849 to 9858.

The intermediate 10 (90 mg, 155 μmol), the intermediate 11 (201 mg, 155 μmol), tri(o-tolyl)phosphine (P(o-tolyl)₃: 3.8 mg, 12.4 μmol), tris(dibenzylideneacetone)dipalladium (Pd₂(dba)₃: 3.1 mg, 3.1 μmol), and dehydrated chlorobenzene (5 mL) were mixed with each other and stirred in a nitrogen atmosphere at 130° C. for 24 hours. The reaction solution was cooled to room temperature, was poured into a methanol (40 mL)/concentrated hydrochloric acid (2 mL) mixed solution, and was stirred for 2 hours. Precipitates were separated by filtration and were cleaned with methanol. The obtained crude product was sequentially Soxhlet-extracted with methanol, acetone, and hexane, and soluble impurities were removed. Next, the reaction product was Soxhlet-extracted with chloroform, the obtained solution was concentrated under a reduced pressure, and methanol was added thereto. Precipitated solids were separated by filtration, were cleaned with methanol, and were dried in a vacuum at 80° C. for 12 hours. As a result, a polymer 9 (195 mg) was obtained.

In the polymer 9, the number-average molecular weight in terms of polystyrene was 1.9×10⁴, and the weight-average molecular weight was 4.6×10⁴.

Synthesis Example 3 Synthesis of Polymers 1, 3 to 8, and 10 to 21

Under the same conditions as in Synthesis Example 1 or 2, each of polymers 1, 3 to 8, and 10 to 2 was synthesized.

<Compounds for Comparison>

Comparative compounds 1 to 5 shown below were prepared.

The comparative compound 1 was a compound described in JP2013-197193A.

The comparative compound 2 was a compound A described in JP2015-048346A.

The comparative compound 3 was poly(3-hexylthiophene-2,5-diyl) (manufactured by Sigma-Aldrich Corporation).

Each of the comparative compounds 4 and 5 was synthesized under the same conditions as in Synthesis Example 1 or 2.

Preparation Example of Organic Semiconductor Composition

3 mg of the polymer or the comparative compound shown in Table 1 and 1 mL of chlorobenzene were put into a glass vial and were mixed with each other and stirred using a Mix rotor (manufactured by AS ONE Corporation) at 60° C. for 12 hours. Next, the obtained solution was filtered through a membrane filter having a pore size of 0.5 μm. This way, organic semiconductor compositions 1 to 21 according to the embodiment of the present invention and comparative organic semiconductor compositions c1 to c5 were prepared.

The content of the polymer in each of the compositions was 0.27 mass %.

Example 1

The bottom gate-bottom contact type organic thin film transistor element 100 shown in FIG. 1 was manufactured, and characteristics thereof were evaluated.

<Manufacturing of Organic Thin Film Transistor Element>

Aluminum was deposited on a glass substrate (EAGLE XG: manufactured by Corning Inc., thickness: 1.1 mm) to form a gate electrode (thickness: 50 nm). A gate insulating film-forming composition (polyvinyl phenol/2,4,6-tris[bis(metboxymethyl)amino]-1,3,5-triazine=1 part by mass/1 part by mass of PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2 mass %)) was spin-coated on the gate electrode and was baked (heated and dried) at 150° C. for 60 minutes to form a gate insulating film having a thickness of 400 nm.

Next, silver ink (SILVER NANOCOLLOID H-1 (trade name), manufactured by Mitsubishi Materials Corporation) was printed (drawn) on the gate insulating film using an ink jet device: DMP-2831 (trade name, manufactured by Fuji Film Dimatix Inc.) in a shape of a source electrode and a drain electrode (thickness: about 100 nm, gate length: 60 μm, gate width: 200 μm). Next, the silver ink was baked using an oven at 180° C. for 30 minutes and was sintered to form the source electrode and the drain electrode. This way, an element precursor was obtained.

In a nitrogen glove box, each of the organic semiconductor composition shown in Table 1 was spin-coated (at 500 rpm for 10 seconds and further at 1000 rpm for 30 seconds) on the element precursor and was dried on a hot plate at 100° C. for 1 hour to form an organic semiconductor layer (thickness: about 20 nm). This way, each of organic thin film transistor elements T1 to T21 according to the embodiment of the present invention and comparative organic thin film transistor elements CT1 to CT5 was manufactured.

Regarding each of the organic thin film transistor elements, 10 specimens for carrier mobility measurement were manufactured.

The content of the polymer in each of the organic semiconductor layers was 100 mass %.

<Evaluation of Organic Thin Film Transistor Element>

Regarding each of the manufactured organic thin film transistor elements, the following performance evaluation was performed in air using a semiconductor characteristic evaluation device: B2900A (trade name, manufactured by Agilent Technologies Inc.). The results are shown in Table 1.

(Evaluation of Variation (Uniformity) in Carrier Mobility)

1. Measurement of Carrier Mobility μ^(AV)

Regarding each of the organic thin film transistor elements T1 to T21 and CT1 to CT5, the carrier mobilities of all the 10 manufactured specimens for carrier mobility measurement were measured. Specifically, a voltage of −50 V was applied between the source electrode and the drain electrode of each of the organic thin film transistor elements, a gate voltage was caused to vary in a range of +10 V to −70 V, and a carrier mobility μ (cm²/Vs) was calculated using the following expression indicating a drain current I_(d). An average value of the cancer mobilities of the 10 specimens was calculated as a carrier mobility μ^(AV). Regarding the carrier mobility μ^(AV), the results of the organic thin film transistor elements T1 to T21, CT-3, and CT-4 are shown in Table 1.

The higher the carrier mobility μ^(AV), the better. In this test, it is preferable that the carrier mobility μ^(AV) is 1×10⁻² cm²/Vs or higher. I _(d)=(w/2L)μC _(j)(V _(g) −V _(th))²

In the expression, L represents the gate length, w represents the gate width, μ represents the carrier mobility, C₁ represents the volume of the gate insulating layer per unit area V_(g) represents the gate voltage, and V_(th) represents a threshold voltage.

2. Calculation of Variation Coefficient

Regarding each of the organic thin film transistor elements T1 to T21 and CT1 to CT5, a variation coefficient was calculated from the following expression using the carrier mobilities of the 10 specimens in the “measurement of the carrier mobility μ”.

In the following expression, a standard deviation was calculated using an ordinary method, and the carrier mobility μ^(AV) was used as an average value.

This variation coefficient was evaluated as an index indicating a variation in carrier mobility. An evaluation rank to which the obtained variation coefficient belongs was determined among the following evaluation ranks. The lower the variation coefficient, the lower the variation in mobility between the specimens. In this test, Rank A or B is preferable, and Rank A is more preferable, Variation Coefficient (%)=(Standard Deviation/Average Value)×100

“A”: lower than 15%

“B”: 15% or higher and lower than 30%

“C”: 30% or higher and lower than 50%

“D”: 50% or higher

(Evaluation of Heat Resistance)

Regarding each of the organic thin film transistor elements T1 to T21 and CT1 to CT5 each of the 10 specimens for carrier mobility measurement was heated in a nitrogen glove box at 150° C. for 1 hour. Next, under the same conditions as in “the measurement of carrier mobility μ^(AV)”, carrier mobilities μm after heating were measured, and an average value of the carrier mobilities of the 10 specimens was calculated as a carrier mobility μ_(H) ^(AV) after heating.

A carrier mobility maintaining ratio (%) was obtained from the following expression based on the obtained carrier mobility U_(H) ^(AV) after heating and the obtained carrier mobility μ^(AV). An evaluation rank to which the obtained carrier mobility maintaining ratio (%) belongs was determined among the following evaluation ranks. The higher the carrier mobility maintaining ratio, the higher the heat resistance. In this test, Rank B or higher is preferable, and Rank A or higher is more preferable. Carrier Mobility Maintaining Ratio (%)=(Carrier mobilityafter Heating/Carrier Mobility μ^(AV))×100

“A”: 80% or higher

“B”: 60% or higher and lower than 80%

“C”: 40% or higher and lower than 60%

“D”: 40% or higher

TABLE 1 Polymer Carrier Element Organic Semiconductor Weight-Average Mobility μ^(AV) Variation in Heat No. Composition No. No. Molecular Weight ×10⁻² (cm²/Vs) Carrier Mobility Resistance Note T1 1 1 35,000 2.7 A B Present Invention T2 2 2 46,000 2.5 A B Present Invention T3 3 3 39,000 2.9 A B Present Invention T4 4 4 32,000 2.8 A A Present Invention T5 5 5 30,000 2.6 A A Present Invention T6 6 6 56,000 2.8 A A Present Invention T7 7 7 33,000 2.5 A A Present Invention T8 8 8 47,000 6.6 A A Present Invention T9 9 9 46,000 6.5 A A Present Invention T10 10 10 42,000 5.2 A A Present Invention T11 11 11 44,000 4.5 A A Present Invention T12 12 12 39,000 3.1 A A Present Invention T13 13 13 52,000 4.2 A A Present Invention T14 14 14 52,000 3.3 A A Present Invention T15 15 15 53,000 2.8 A A Present Invention T16 16 16 32,000 2.0 A A Present Invention T17 17 17 39,000 3.4 A A Present Invention T18 18 18 34,000 1.2 A B Present Invention T19 19 19 29,000 2.5 A B Present Invention T20 20 20 25,000 1.8 A A Present Invention T21 21 21 47,000 5.8 A A Present Invention CT1 c1 Comparative 284 — D D Comparative Compound 1 Example CT2 c2 Comparative 425 — D D Comparative Compound 2 Example CT3 c3 Comparative 52,000 0.10 B D Comparative Compound 3 Example CT4 c4 Comparative 23,000 0.05 B D Comparative Compound 4 Example CT5 c5 Comparative 9,000 — D D Comparative Compound 5 Example

The following can be seen from the results of Table 1.

Each of the organic thin film transistor elements CT1 to CT5 included the organic semiconductor layer including the comparative compound, and thus did not have high carrier mobility, uniformity thereof, and high heat resistance.

That is, in the organic thin film transistor elements CT1 and CT2 that included the organic semiconductor layers including the comparative compounds 1 and 2 as dinaphthothiophene compounds, a variation in carrier mobility was large, and the carrier mobility significantly decreased after heating. Further, in the organic thin film transistor elements CT3 and CT4, the organic semiconductor layer included polymers, respectively. However, these polymers included a repeating unit not having a group derived from the dinaphtho chalcogenophene compound. Therefore, the organic thin film transistor elements including these polymers had low carrier mobility μ^(AV) and low heat resistance. On the other hand, the organic thin film transistor element CT5 included the organic semiconductor layer that included the polymer consisting of only the group derived from the dinaphtho chalcogenophene compound, and was not sufficient from the viewpoints of the variation in carrier mobility and heat resistance.

On the other hand, the organic thin film transistor elements T1 to T21 according to the embodiment of the present invention included the organic semiconductor layer including the polymer according to the embodiment of the present invention, and thus had high carrier mobility, uniformity thereof, and high heat resistance.

In particular, in a case where the polymer including the aromatic heterocyclic group represented by A¹² in Formula (2) was included, the heat resistance was able to be further improved while maintaining the carrier mobility and uniformity thereof (element Nos. T4 to T17, T20, and T21).

In addition, in a case where A¹² in Formula (2) was the aromatic heterocyclic group represented by Formula (A-3), the effect of improving the carrier mobility was high, and high carrier mobility, uniformity thereof, and high heat resistance were able to be obtained with a good balance (Element Nos. T8 to T10, and T21).

Further, in a case where both A11 and A13 in Formula (2) were the aromatic heterocyclic groups represented by Formula (Ar-1), the carrier mobility was able to be significantly improved (Element Nos. T9 and T20).

In a case where the polymer in which Y¹ in Formula (1) was an oxygen atom is compared to the polymer in which Y¹ in Formula (1) was a sulfur atom, the same performance was exhibited from the viewpoints of uniformity of carrier mobility and heat resistance, but the polymer in which Y¹ in Formula (1) was a sulfur atom exhibited higher performance from the viewpoint of carrier mobility (Element Nos. T9 and T21).

The present invention has been described using the embodiments. However, unless specified otherwise, any of the details of the above description is not intended to limit the present invention and can be construed in a broad sense within a range not departing from the concept and scope of the present invention disclosed in the accompanying claims.

The present application claims priority based on JP2016-074079 filed on Apr. 1, 2016, the entire content of which is incorporated herein by reference.

EXPLANATION OF REFERENCES

-   -   10: substrate     -   20: gate electrode     -   30: gate insulating film     -   40: source electrode     -   42: drain electrode     -   50: organic semiconductor film     -   60: sealing layer     -   100, 200: organic thin film transistor element 

What is claimed is:
 1. An organic semiconductor element comprising: an organic semiconductor film that includes a polymer having a repeating unit represented by the following Formula (1),

in Formula (1), Y¹ represents an oxygen atom, a sulfur atom, or a selenium atom, R¹¹ to R¹⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 3, r and s each independently represent an integer of 0 to 2, A¹⁰ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and m¹⁰ represents an integer of 1 to 12, wherein the polymer comprises at least 2 of the repeating units.
 2. The organic semiconductor element according to claim 1, wherein the repeating unit is represented by the following Formula (2),

in Formula (2), Y¹, R¹¹ to R¹⁴, a, b, r, and s have the same definitions as Y¹, R¹¹ to R¹⁴, a, b, r, and s in Formula (1), respectively, A¹¹ and A¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group other than aromatic heterocyclic groups represented by the following Formulae (A-1) to (A-12), a vinylene group, or an ethynylene group, A¹² represents an aromatic heterocyclic group represented by any one of the following Formulae (A-1) to (A-12), m¹¹ and m¹³ each independently represent an integer of 0 to 4, m¹² represents an integer of 0 to 4, and the sum of m¹¹, m¹², and m¹³ is 1 or more,

in Formulae (A-1) to (A-12), X^(A)'s each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR^(X), R^(N) and R^(X) each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain or a group represented by the following Formula (1-1), Y^(A)'s each independently represent an oxygen atom or a sulfur atom, Z^(A)'s each independently represent CR^(A2) or a nitrogen atom, W^(A)'s each independently represent C(R^(A2))₂, NR^(A1), a nitrogen atom, CR^(A2), an oxygen atom, a sulfur atom, or a selenium atom, R^(A1)'s each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, a group represented by the following Formula (1-1), or a single bond, R^(A2)'s each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, or a single bond, R^(A3)'s each independently represent a hydrogen atom or a substituent, and * represents a binding site to another group forming the repeating unit, and

in Formula (1-1), L_(a) represents an alkylene group having 1 to 20 carbon atoms which may have at least one of —O—, —S—, or —NR^(1S)— in a carbon chain, Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, L_(b) represents an alkyl group having 1 to 100 carbon atoms which may have at least one of —O—, —S—, or —NR^(2S)— in a carbon chain, R^(1S) and R^(2S) each independently represent a hydrogen atom or a substituent, l represents an integer of 1 to 5, and * represents a binding site to a ring-constituting nitrogen atom in Formula (A-1) or (A-2), a nitrogen atom in NR^(X) of X^(A), or a nitrogen atom in NR^(A1) of W^(A).
 3. The organic semiconductor element according to claim 2, wherein m¹² represents an integer of 1 to
 4. 4. The organic semiconductor element according to claim 2, wherein and -(A¹¹)m¹¹- and -(A¹³)m¹³- are each independently represented by the following Formula (Ar-1),

in Formula (Ar-1), X^(d) represents an oxygen atom, a sulfur atom, a selenium atom, or NR^(D1), Z^(d)'s each independently represent a nitrogen atom or CR^(D2), R^(D1) and R^(D2) represent a hydrogen atom or a substituent, m^(d) represents an integer of 1 to 4, and * represents a binding site to another group forming the repeating unit.
 5. The organic semiconductor element according to claim 4, wherein X^(d) represents a sulfur atom, and all the Z^(d)'s represent CR^(D2).
 6. The organic semiconductor element according to claim 1, wherein the organic semiconductor element is an organic thin film transistor element.
 7. A polymer comprising: a repeating unit represented by the following Formula (1),

in Formula (1), Y¹ represents an oxygen atom, a sulfur atom, or a selenium atom, R¹¹ to R¹⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 3, r and s each independently represent an integer of 0 to 2, A¹⁰ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and m¹⁰ represents an integer of 1 to 12, wherein the polymer comprises at least 2 of the repeating units.
 8. The polymer according to claim 7, wherein the repeating unit is represented by the following Formula (2),

in Formula (2), Y¹, R¹¹ to R¹⁴, a, b, r, and s have the same definitions as Y¹, R¹¹ to R¹⁴, a, b, r, and s in Formula (1), respectively, A¹¹ and A¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group other than aromatic heterocyclic groups represented by the following Formulae (A-1) to (A-12), a vinylene group, or an ethynylene group, A¹² represents an aromatic heterocyclic group represented by any one of the following Formulae (A-1) to (A-12), m¹¹ and m¹³ each independently represent an integer of 0 to 4, m¹² represents an integer of 0 to 4, and the sum of m¹¹, m¹², and m¹³ is 1 or more,

in Formulae (A-1) to (A-12), X^(A)'s each independently represent an oxygen atom, a sulfur atom, a selenium atom, or NR^(X), R^(N) and R^(X) each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain or a group represented by the following Formula (1-1), Y^(A)'s each independently represent an oxygen atom or a sulfur atom, Z^(A)'s each independently represent CR^(A2) or a nitrogen atom, W^(A)'s each independently represent C(R^(A2))₂, NR^(A1), a nitrogen atom, CR^(A2), an oxygen atom, a sulfur atom, or a selenium atom, R^(A1)'s each independently represent an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, a group represented by the following Formula (1-1), or a single bond, R^(A2)'s each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have at least one of —O—, —S—, or —NR^(A3)— in a carbon chain, or a single bond, R^(A3)'s each independently represent a hydrogen atom or a substituent, and * represents a binding site to another group forming the repeating unit, and

in Formula (1-1), L_(a) represents an alkylene group having 1 to 20 carbon atoms which may have at least one of —O—, —S—, or —NR^(1s)— in a carbon chain, Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, L_(b) represents an alkyl group having 1 to 100 carbon atoms which may have at least one of —O—, —S—, or —NR^(2S)— in a carbon chain, R^(1S) and R^(2S) each independently represent a hydrogen atom or a substituent, l represents an integer of 1 to 5, and * represents a binding site to a ring-constituting nitrogen atom in Formula (A-1) or (A-2), a nitrogen atom in NR^(X) of X^(A), or a nitrogen atom in NR^(A1) of W^(A).
 9. The polymer according to claim 8, wherein m¹² represents an integer of 1 to
 4. 10. The polymer according to claim 8, wherein and -(A¹¹)m¹¹- and -(A¹³)m¹³- are each independently represented by the following Formula (Ar-1),

in Formula (Ar-1), X^(d) represents an oxygen atom, a sulfur atom, a selenium atom, or NR^(D1), Z^(d)'s each independently represent a nitrogen atom or CR^(D2), R^(D1) and R^(D2) represent a hydrogen atom or a substituent, m^(d) represents an integer of 1 to 4, and * represents a binding site to another group forming the repeating unit.
 11. The polymer according to claim 10, wherein X^(d) represents a sulfur atom, and all the Z^(d)'s represent CR^(D2).
 12. An organic semiconductor composition comprising: the polymer according to claim 7; and a solvent.
 13. An organic semiconductor film comprising: the polymer according to claim
 7. 14. The organic semiconductor element according to claim 1, wherein the polymer comprises at least 10 of the repeating units.
 15. The polymer according to claim 7, wherein the polymer comprises at least 10 of the repeating units. 